CN108046234B - Improve the charcoal method for fine finishing of anaerobic organism reaction efficiency - Google Patents

Improve the charcoal method for fine finishing of anaerobic organism reaction efficiency Download PDF

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CN108046234B
CN108046234B CN201711135985.9A CN201711135985A CN108046234B CN 108046234 B CN108046234 B CN 108046234B CN 201711135985 A CN201711135985 A CN 201711135985A CN 108046234 B CN108046234 B CN 108046234B
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charcoal
reaction efficiency
anaerobic
anaerobic organism
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CN108046234A (en
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吕凡
何品晶
邵立明
章骅
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/023—Methane
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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Abstract

The present invention relates to the charcoal method for fine finishing for improving anaerobic organism reaction efficiency.Coarse biometric charcoal is handled as follows in this method: coarse biometric charcoal is crushed to certain particle size range, obtains super fine biological charcoal；It carries out embathing processing by dip lotion through above-mentioned smashed super fine biological charcoal.When the anaerobic organisms reactions such as the charcoal for finishing acquisition by the method for the invention is applied to anaerobic digestion, carbochain biology extends, synthesis gas fermentation, it is remarkably improved anaerobic organism reaction efficiency, improve the conspicuousness of charcoal Application effect and the stability of effect, dosage when charcoal application is reduced, application cost is reduced.

Description

Improve the charcoal method for fine finishing of anaerobic organism reaction efficiency
Technical field
The invention belongs to environmental protections and comprehensive utilization of resources field, are related to one kind to be applied to anaerobism conversion process as mesh Charcoal method for fine finishing.
Background technique
Anaerobic organism reaction applied to environmental resource field is mainly " anaerobic digestion ", by the organic matter degradation in waste It is converted to methane and carbon dioxide.And " biorefining " technology developed in recent years is then more emphasized to synthesize more using waste as raw material The chemicals of high resource value, for example, carbochain biology elongation technology is to be converted to short carbon chain organic acid using anaerobe In, Long carbon chain organic acid；Synthesis gas fermentation technique be using anaerobe by refuse-derived synthesis gas be converted to methane and acid, Alcohol product.
Due to anaerobe slow growth, to environmental parameter change it is extremely sensitive, anaerobic digestion, carbochain biology Extend, synthesis gas ferment these anaerobic organisms react generally existing conversion ratio it is low, vulnerable to matrix or Product inhibiton, fluctuation of service The problem of.Many researchers, which are proposed, in the recent period is applied to anaerobic organism reaction process for charcoal made from waste pyrolysis, To improve the technical thought of system effectiveness.Such as: Chinese invention patent is [a kind of to promote anaerobic sludge digestion methane phase using charcoal Method publication number: CN 104150730A] partial size < 0.5mm charcoal powder is added to anaerobic digestion reaction vessel；Middle promulgated by the State Council Bright patent [a kind of method publication number for promoting solid organic castoff to produce biogas using composite material: CN 102061254A] will 10-500 μm of partial size of charcoal and medical stone mixing material is as additive, for promoting the anaerobism of solid organic castoff to send out Ferment；Document [Barua, S., Dhar, B.R.2017.Advances towards understanding and engineering direct interspecies electron transfer in anaerobic digestion.Bioresource Technology, 244 (Part 1), 698-707.] and [Romero-G ü iza, M.S., Vila, J., Mata-Alvarez, J., Chimenos,J.M.,Astals,S.2016.The role of additives on anaerobic digestion:A Review.Renewable and Sustainable Energy Reviews, 58,1486-1499.] it reviews over nearly 5 years Charcoal as additive organic matter anaerobic digestion process application；A kind of Chinese invention patent [raising carbochain biology extension The method publication number of Product formation concentration: 105755059 A of CN] it proposes to utilize electric conductivity of the grain diameter less than 100 microns Carbon based material synthesizes concentration to improve carbochain biology extension products；Chinese invention patent is [a kind of to improve synthesis gas using carbon material The method .CN107130003A of anaerobic fermentation effect] it proposes to be not less than 100m using partial size < 150 micron, specific surface area2/ g or Person's soda acid functional group content is not less than the carbon material of 3mmol/g to improve synthesis gas anaerobic fermentation effect.
But charcoal exists uncertain in the practical application effect that anaerobic organism reacts.For example, document [Y.Shen, J.L.Linville,P.A.A.Ignacio-de Leon,R.P.Schoene,M.Urgun-Demirtas,Towards a sustainable paradigm of waste-to-energy process:Enhanced anaerobic digestion Of sludge with woody biochar, J.Clean Prod.135 (2016) 1054-1064.] find that charcoal adds Anaerobic digestion efficiency can be reduced when measuring excessive instead；Document [J.Cai, P.J.He, Y.Wang, L.M.Shao, F.L ü, Effects and optimization of the use of biochar in anaerobic digestion of food wastes, Waste Manage.Res.34 (5) (2016) 409-416.] it finds when the vigor of anaerobic digestion microorganism is natively very high, The effect for adding charcoal is not very significant.The effect that charcoal influences anaerobic organism reaction depends on the property of charcoal itself Matter, and the property of charcoal is influenced by many factors, including prepare charcoal raw material (hardwood, cork, bamboo branch, stalk, Sludge etc.), pyrolytical condition (temperature, time etc.).Therefore, the charcoal property for influencing anaerobic organism reaction most critical should be picked out Feature, the corresponding finishing for carrying out charcoal reduce charcoal and answer to improve the Application effect of charcoal and the stability of effect The dosage of used time reduces application cost.
Summary of the invention
Based on above-mentioned technical background, the invention proposes a kind of charcoals for the purpose of improving anaerobic organism reaction efficiency Universality method for fine finishing.The charcoal prepared by this method achieves noticeable achievement, surely when being applied to anaerobic organism reaction It is fixed.
The purpose of the present invention can be achieved through the following technical solutions:
Improve anaerobic organism reaction efficiency charcoal method for fine finishing, which is characterized in that this method to coarse biometric charcoal into The following processing of row:
(1) size controlling: coarse biometric charcoal is crushed to the particle size range of 150nm~5 μm, obtains super fine biological charcoal；
(2) processing is embathed on surface: being carried out embathing processing by dip lotion through above-mentioned smashed super fine biological charcoal, be mentioned The charcoal of high anaerobic organism reaction efficiency；Embathing formula of liquid is: NH4H2PO43-4g/L, NaHCO34.5-5.5g/L MgCl2·6H2O 0.2-0.4g/L, MgSO4·7H2O 0.1-0.3g/L, KCl 0.1-0.2g/L, CaCl2·2H2O 0.1- 0.3g/L。
Preferably, embathing formula of liquid is: NH4H2PO43.6g/L, NaHCO35.04g/L MgCl2·6H2O 0.33g/L, MgSO4·7H2O 0.2g/L, KCl 0.15g/L, CaCl2·2H2O 0.2g/L。
Preferably, embathing solid-to-liquid ratio is 1:3~1:10.
Preferably, embathing the time is 8~24 hours.
Preferably, hunting speed is 100~150rpm when embathing.
Preferably, rear drying and processing is embathed.
Preferably, the coarse biometric charcoal is the pyrolytic carbon obtained after the pyrolysis of biomass class raw material.Biomass class is former Material is including fruit tree etc..
When the charcoal that the method for the present invention obtains is reacted for anaerobic organism, charcoal dosage is 15-20g/L.
The present invention also provides several applications that charcoal is used for anaerobic organism reaction, are certainly not limited to these applications:
Charcoal is applied to anaerobism carbochain biology extension system, and charcoal dosage is 20g/L,
Charcoal is applied to the Anaerobic Digestion of refuse landfill initial leachate, and charcoal dosage is 16g/L,
Charcoal is applied to the Anaerobic Digestion of kitchen garbage slurries, and charcoal dosage is 16g/L.
Compared with prior art, key problem in technology of the invention is:
1, partial size be 150nm~5 μm super fine biological charcoal in physicochemical properties significant difference in some tens of pm partial size Above charcoal.Other than specific grain surface product, distribution of pores change, the electric conductivity of charcoal particle surface, electricity The properties such as son storage and transmission characteristic grow exponentially, and functional group distribution also changes, thus raw being applied to anaerobism When object reacts, it is more advantageous to electron transmission between promoting microbial species, shows promotion advantage outstanding.And size controlling exists 150nm or more avoids the toxicity that nano material may cause microbial cell, avoids reacting inverse to anaerobic organism Effect.
2, super fine biological charcoal after crushed further takes surface to embathe processing, can remove charcoal and prepare in pyrolysis When a large amount of volatile organic compounds for depositing, avoid its from inhibiting anaerobe.What is used embathes formula of liquid and can accelerate these The leaching of toxic organics balances, and it is avoided further to be immersed when subsequent bio charcoal is applied to anaerobic organism reaction Out.
Detailed description of the invention
Principal component analysis result of the Fig. 1 based on 10 kinds of each physical and chemical parameters of different-grain diameter charcoal；
Fig. 2 carboxylic acid forms the rule that changes with time.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
For coarse biometric charcoal from 500 DEG C of fruit tree pyrolysis, 2 hours pyrolytic carbons obtained, initial particle range is 2-5mm.It utilizes Coarse biometric charcoal is ground into the super fine biological charcoal that partial size is 1~5 μm by airslide disintegrating mill.By the super fine biological charcoal and same source but The charcoal (5000~2000,2000~1000,1000~500,500~250,250~150,150~75,75 of different-grain diameter ~45,45~25,25~16 μm) it carries out property analysis and compares, comprising: C/H/O/N elemental analysis, X-ray fluorescence spectra XRF, X-ray diffraction XRD, Fourier transform infrared spectroscopy FTIR, scanning electron microscope sem, specific surface area, pore-size distribution, oxygen-containing official Energy group, real density, infusion dissolved organic carbon compound, electric conductivity and zwitterion concentration etc.；Subsequently, based on above each Item index test is as a result, using principal component multidimensional statistics analysis method, and these data reduction dimensionality reductions, generalized analysis is different Partial size charcoal is in physical and chemical qualitative difference, as shown in Figure 1, showing in the physicochemical property of the super fine biological charcoal (P5) of < 5 μm of partial sizes Write the charcoal particle different from other partial sizes.
It carries out embathing processing by dip lotion through above-mentioned smashed super fine biological charcoal, embathing solid-to-liquid ratio is 1:3, when embathing Between be 24 hours, when embathing hunting speed be 120rpm, embathing formula of liquid is: NH4H2PO43.6g/L, NaHCO35.04g/L MgCl2·6H2O 0.33g/L, MgSO4·7H2O 0.2g/L, KCl 0.15g/L, CaCl2·2H2O 0.2g/L.105 after embathing DEG C drying, drying at room temperature save.Content of volatile organic compound before embathing on charcoal is 59mg/kg, is reduced to after embathing 4.9mg/kg。
It is applied to anaerobism carbochain biology extension system, dosage 20g/L through charcoal made from above-mentioned finishing. As shown in Fig. 2, in reaction the 10th day, the sour accounting of target product has surpassed after the super fine biological charcoal (P5) of < 5 μm of partial sizes adds 80% is crossed, other large-sized charcoal groups are significantly higher than.And with the extension of reaction time, caproic acid institute in all carboxylic acids The ratio accounted for is gradually increased.To the 31st day, accounting of the caproic acid of P5 group in all carboxylic acids was 92.6%, and remaining each group oneself Proportional region of the acid in all carboxylic acids is 23% -33%.Therefore, the biology obtained by adding the method for the present invention finishing Charcoal can greatly improve the target product selection rate of anaerobism carbochain biology extension and generate rate.
Embodiment 2
The finishing condition of charcoal is same as Example 1.It is filled out through charcoal made from above-mentioned finishing applied to rubbish The Anaerobic Digestion of an initial leachate is buried, charcoal dosage is 16g/L, and the COD concentration of percolate is 28000mg/L. The peak methane-producing rate for being not added with the blank group of charcoal is 18mL-CH4/ g-COD/d, and it is added to the method for the present invention finishing The peak methane-producing rate of the experimental group for the charcoal that work obtains is 51mL-CH4/g-COD/d.As control, it is added to partial size Peak methane-producing rate for the control group that 75-150 μm of charcoal and partial size are 2-5mm charcoal is respectively 36mL-CH4/g- COD/d and 34mL-CH4/g-COD/d。
Embodiment 3
The finishing condition of charcoal is same as Example 1.It is applied to kitchen rubbish through charcoal made from above-mentioned finishing The Anaerobic Digestion of rubbish slurries, charcoal dosage are 16g/L, and the COD concentration of slurries is 82000mg/L.Due to slurries Organic loading is excessively high, seriously inhibits the vigor of methanogen, and as a result for being not added with the blank group of charcoal, the lag phase is long Up to 28 days, and it is added to the experimental group for the charcoal that the method for the present invention finishing obtains, the lag phase shorten to 9 days.As right According to, be added to partial size be 75-150 μm of charcoal and partial size be 2-5mm charcoal control group lag phase be respectively 15 days and 18 days.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention. Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention Within protection scope.

Claims (9)

1. improving the charcoal method for fine finishing of anaerobic organism reaction efficiency, which is characterized in that this method carries out coarse biometric charcoal Following processing:
(1) size controlling: coarse biometric charcoal is crushed to 1~5 μm of particle size range, obtains super fine biological charcoal；
(2) processing is embathed on surface: being carried out embathing processing by dip lotion through above-mentioned smashed super fine biological charcoal, is improved and detests The charcoal of oxygen biological respinse efficiency；
Embathing formula of liquid is: NH4H2PO43-4g/L, NaHCO34.5-5.5g/L, MgCl2·6H2O 0.2-0.4g/L, MgSO4·7H2O 0.1-0.3g/L, KCl 0.1-0.2g/L, CaCl2·2H2O 0.1-0.3g/L。
2. improving the charcoal method for fine finishing of anaerobic organism reaction efficiency according to claim 1, which is characterized in that embathe Formula of liquid is: NH4H2PO43.6g/L, NaHCO35.04g/L MgCl2·6H2O 0.33g/L, MgSO4·7H2O 0.2g/L, KCl 0.15g/L, CaCl2·2H2O 0.2g/L。
3. improving the charcoal method for fine finishing of anaerobic organism reaction efficiency according to claim 1, which is characterized in that embathe Solid-to-liquid ratio is 1:3~1:10.
4. improving the charcoal method for fine finishing of anaerobic organism reaction efficiency according to claim 1, which is characterized in that embathe Time is 8~24 hours.
5. improving the charcoal method for fine finishing of anaerobic organism reaction efficiency according to claim 1, which is characterized in that embathe When hunting speed be 100~150rpm.
6. improving the charcoal method for fine finishing of anaerobic organism reaction efficiency according to claim 1, which is characterized in that embathe Drying and processing afterwards.
7. improving the charcoal method for fine finishing of anaerobic organism reaction efficiency according to claim 1, which is characterized in that described Coarse biometric charcoal is the pyrolytic carbon obtained after the pyrolysis of biomass class raw material.
8. the charcoal that method as described in claim 1 obtains is reacted for anaerobic organism, which is characterized in that charcoal dosage For 15-20g/L.
9. charcoal is reacted for anaerobic organism according to claim 8, which is characterized in that including applying below:
Charcoal is applied to anaerobism carbochain biology extension system, and charcoal dosage is 20g/L,
Charcoal is applied to the Anaerobic Digestion of refuse landfill initial leachate, and charcoal dosage is 16g/L,
Charcoal is applied to the Anaerobic Digestion of kitchen garbage slurries, and charcoal dosage is 16g/L.
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CN109368986A (en) * 2018-12-06 2019-02-22 齐鲁工业大学 It is a kind of to promote excess sludge digestion production H using charcoal2The method of yield
CN109761215B (en) * 2019-03-11 2022-05-10 大连理工大学 Preparation method of kitchen waste-based composite defective conductive porous carbon material
CN111438159A (en) * 2020-03-11 2020-07-24 上海交通大学 Kitchen waste treatment system and treatment method

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CN104772146A (en) * 2015-03-18 2015-07-15 昆明理工大学 Preparation method of modified bio-charcoal based catalyst
CN105536704A (en) * 2016-01-11 2016-05-04 湖南大学 Calcium modified biochar and preparation method and application thereof
CN105664874A (en) * 2016-04-10 2016-06-15 武汉沃特工程技术有限公司 Biochar adsorbing agent for removing nitrate nitrogen in solution and preparing method thereof

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Publication number Priority date Publication date Assignee Title
CN104772146A (en) * 2015-03-18 2015-07-15 昆明理工大学 Preparation method of modified bio-charcoal based catalyst
CN105536704A (en) * 2016-01-11 2016-05-04 湖南大学 Calcium modified biochar and preparation method and application thereof
CN105664874A (en) * 2016-04-10 2016-06-15 武汉沃特工程技术有限公司 Biochar adsorbing agent for removing nitrate nitrogen in solution and preparing method thereof

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